Methyl ricinoleate as platform chemical for simultaneous production of fine chemicals and polymer precursors

Article abstract of DOI:10.1002/cssc.201200320

The modification of methyl ricinoleate by etherification of the hydroxyl group was accomplished by using a nonclassical ruthenium-catalyzed allylation reaction and also by esterification. Methyl ricinoleate derivatives were engaged in ring-closing metathesis (RCM) reactions leading to biosourced 3,6-dihydropyran and α,β-unsaturated lactone derivatives with concomitant production of polymer precursors. Sequential RCM/hydrogenation and RCM/cross-metathesis were also implemented as a straightforward method for the synthesis of tetrahydropyran and lactone derivatives as well as valuable monomers (i.e., polyamide precursors).

Full text of DOI:10.1002/cssc.201200320

DOI: 10.1002/cssc.201200320
Methyl Ricinoleate as Platform Chemical for Simultaneous
Production of Fine Chemicals and Polymer Precursors
Antoine Dupꢀ,[a, b] Mathieu Achard,[a] Cꢀdric Fischmeister,*[a] and Christian Bruneau*[a]
The modification of methyl ricinoleate by etherification of the
hydroxyl group was accomplished by using a nonclassical
ruthenium-catalyzed allylation reaction and also by esterifica-
tion. Methyl ricinoleate derivatives were engaged in ring-clos-
ing metathesis (RCM) reactions leading to biosourced 3,6-dihy-
dropyran and a,b-unsaturated lactone derivatives with con-
comitant production of polymer precursors. Sequential RCM/
hydrogenation and RCM/cross-metathesis were also imple-
mented as a straightforward method for the synthesis of tetra-
hydropyran and lactone derivatives as well as valuable mono-
mers (i.e., polyamide precursors).
Introduction
The sustainable utilization of biomass as a renewable source of
raw materials is a domain of strong economic and environ-
mental interest in a context of fossil-resource shortage.[1]
Owing to their long carbon chains, fatty acid methyl esters
(FAMEs) offer interesting perspectives for the polymer indus-
try[2] and for the preparation of surfactants.[3] Typically, these
compounds can be derivatized by C=C bond transformations,
among which efficient and selective catalytic processes are
preferable.[4] Since the early seventies, olefin metathesis has
been used for the transformation of FAMEs,[5] but it is only re-
cently that the incorporation of functional groups by olefin
metathesis was made possible thanks to the development of
highly active and functional-group tolerant catalysts.[6] For ex-
ample, cross-metathesis reactions with methyl acrylate have
been first reported by Meier et al.,[7] whereas our group fo-
cused on cross-metathesis transformations with acrylonitrile to
produce polyamide monomers.[8] In particular, we reported the
direct synthesis of amino esters by a tandem cross-metathesis/
C=C bond and CN hydrogenation reaction.[9] We have become
interested in the transformation of methyl ricinoleate (R-12-hy-
droxy-cis-9-octadecenoic acid methyl ester) as it presents the
double advantage of being a nonedible oil derivative and in-
corporating a hydroxyl functional group, which enables a ther-
mal rearrangement towards the valuable methyl 10-undece-
noate[10] and 1-heptanal.
tives. We show that the choice of catalyst can drive the selec-
tivity of the reaction and that domino ring-closing/cross-meta-
thesis and tandem RCM/hydrogenation can be implemented,
leading to a variety of products of interest for fine chemistry
and polymer synthesis.
Results and Discussion
Methyl ricinoleate derivatization
The allylation of the hydroxyl group of methyl ricinoleate was
attempted by a standard NaH deprotonation in the presence
of allyl bromide, but this method failed to provide the desired
product 2a in good yield due to competitive transesterification
reactions. Other Pd0-catalyzed allylation methods[12] were also
unsuccessful. The catalytic allylation of methyl ricinoleate di-
rectly with branched allyl alcohol was successfully achieved
by extension of
a recently reported procedure using
[RuCp(DPPSA)(h3-propenyl)] (Cp=cyclopentadienyl, DPPSA=
ortho-diphenylphosphinesulfonate) as a catalyst (Scheme 1).[13]
Structural diversity was achieved by the utilization of various
allylic alcohols, which regioselectively provided the products
featuring a terminal allylic group in good to high yields using
2.5–5 mol% of catalyst at 45–1008C. Various solvents including
To the best of our knowledge, the preliminary derivatization
of methyl ricinoleate through the hydroxyl group by ring-clos-
ing metathesis (RCM) has not been reported. We envisioned
that the introduction of allylic ethers or acrylic ester substitu-
ents (Scheme 1) would lead to 3,6-dihydropyran and a,b-unsa-
turated lactone derivatives, which are compounds of interest
in medicine, pharmacology, and flavors.[11] These products
would be obtained with coproduction of methyl 9-decenoate,
another important raw material for the polymer industry
(Scheme 2). Herein, we report on the transformation of methyl
ricinoleate into designed diene derivatives and their RCM reac-
tion leading to dihydropyran and unsaturated lactone deriva-
[a] A. Dupꢀ, Dr. M. Achard, Dr. C. Fischmeister, Dr. C. Bruneau
Institut des Sciences Chimiques de Rennes
Organomꢀtalliques: Matꢀriaux et Catalyse
UMR 6226-CNRS-Universitꢀ de Rennes 1, Campus de Beaulieu
263, avenue du gꢀnꢀral Leclerc. 35042 Rennes (France)
Fax: (+33)223236939
E-mail: cedric.fischmeister@univ-rennes1.fr
christian.bruneau@univ-rennes1.fr
[b] A. Dupꢀ
ADEME
20, avenue du Grꢀsillꢀ
49004 Angers cedex 01 (France)
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201200320.
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C. Fischmeister, C. Bruneau et al.
and 5 obtained in a 1/9 ratio on
the basis of yields calculated by
GC (Scheme 2). As other di-
esters, 5 is an interesting com-
pound for the production of
polyesters[16] and is accessible
by self-metathesis[17] of methyl
oleate or fermentation of oleic
acid.[18–19] In this case, 5 was
most likely obtained by self-
metathesis of 4 producing also
ethylene through a secondary
metathesis reaction rather than
by self-metathesis of the start-
ing 2a because no trace of
7,12-(bis-allyloxy)octadec-8-ene
could be detected.
With this first result we envi-
sioned the same reaction in the
presence of the first generation
Hoveyda catalyst (HI). Indeed,
first generation catalysts are
Scheme 1. Preparation of methyl ricinoleate derivatives.
generally effective for promot-
ing RCM reactions, but they are
dimethyl carbonate (DMC) and diethyl carbonate (DEC) were
used as greener alternatives to the conventional dichlorome-
thane and dichloroethane.[14] The esterification of methyl rici-
noleate was achieved using acryloyl chloride in dichlorome-
thane to yield the desired diester 2e in 75% yield (Scheme 1).
less efficient in promoting cross-metathesis transformations
and should thus lead to the same dihydropyrane 3a and the
two esters 4 and 5, but with a reverse selectivity relative to HII.
Thus, in the reaction of 2a with HI at 508C in DMC for 3 h, 2a
was fully transformed and 3a was again isolated in high yield,
but as anticipated the monoester 4 was now obtained as the
major coproduct (4/5=9:1, Scheme 2). It was thus demonstrat-
ed that it is possible to select one of the reaction products
(polymer precursor) without interfering with the synthesis of
the other product (fine chemical) simply by switching between
first and second generation ruthenium catalysts.
Ring Closing Metathesis transformations
The RCM of 2a was first attempted as a model reaction using
the second generation Hoveyda catalysts (HII) in DMC.[15] This
reaction led almost quantitatively to the desired dihydropyran
(3a) isolated in 99% yield and to the mono- and diesters 4
Scheme 2. RCM of O-allyl methyl ricinoleate.
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Methyl Ricinoleate as a Platform Chemical
Although the molecular struc-
ture of the 3,6-dihydropyran de-
rivative was imposed at the a-
ether position by the nature of
the starting methyl ricinoleate,
molecular diversity was ob-
tained using derivatives 2b–d.
In the presence of HII
(0.5 mol%), these compounds
were efficiently transformed into
the corresponding 3,6-dihydro-
pyrans in high yields with con-
Scheme 3. Synthesis of 3,6-dihydropyran derivatives.
comitant formation of diester 5,
whereas monoester 4 was de-
tected in low amounts as in the
case of 2a (Scheme 3).
The transformation of precur-
sor 2e into the corresponding
a,b-unsaturated lactone was
next attempted.[20] As pointed
out in the literature, the forma-
tion of lactones by RCM does
not perform very well and usual-
ly requires high catalyst loa-
dings.[11b,c,f,20] In our case, cata-
lyst loadings of 3 mol% were
necessary to ensure high con-
versions. When HII was used at
508C in DMC for 14 h, the reac-
Scheme 4. Synthesis of methyl ricinoleate derived a,b-unsaturated lactone.
tion proceeded with full conversion, but led to the formation
of side products arising from double bond migration in the
main chain. HI was thus used in toluene at 808C for 14 h and
indeed furnished a cleaner reaction mixture, but with lower ef-
ficiency (conversion of 45%) leading to 3e in 40% yield. Re-
cently, we[21] and others[22] have reported on a new family of
first generation olefin-metathesis catalysts based on a chelating
indenylidene architecture (Scheme 4, III). More specifically, we
have shown that the combination of high thermal stability and
slow activation of complex III resulted in some cases in im-
proved RCM performance.[21a] Thus, when the RCM of 2e was
attempted with III, the reaction proceeded smoothly reaching
75% conversion in 14 h and furnishing 3e in 72% yield
(Scheme 4). As with the synthesis of 3a in the presence of HI,
4 was the major coproduct (4/5=6:1 by GC analysis). This first
example constitutes an entry towards other unsaturated lac-
tones with molecular diversity in terms of substitution pattern
and ring sizes that could be accessible using the same synthet-
ic strategy.
pose, the RCM reactions of 2a and 2e were repeated as al-
ready described (Scheme 2 and 4) and the crude reaction mix-
tures were transferred into a high pressure reactor. After 14 h
at 758C under H2 (10 bar), products 6 and 7 were isolated in
92 and 66% yield, respectively, with concomitant production
of a mixture of the saturated monoester 8 and diester 9 (8/9=
1:9 by GC analysis for the transformation of 2a and 6:1 by
1H NMR analysis for the transformation of 2e) resulting from
the hydrogenation of 4 and 5, respectively (Scheme 5).
Cascade RCM/cross-metathesis
As mentioned earlier, the RCM reactions of methyl ricinoleate
derivatives 2a–d furnished compounds 3a–d with concomi-
tant formation of mono- and diesters 4 and 5 that are useful
reagents or raw materials for the polymer industry. For exam-
ple, 5 and methyl 10-undecenoate (one extra carbon atom
with regard to 4) have recently been used for the preparation
of polyamide monomers through cross-metathesis reactions
with acrylonitrile.[8a,c,9] Examples of diester synthesis by cross-
metathesis of FAMEs with methyl acrylate have also been re-
cently reported.[7] The synthesis of the same compounds (i.e.,
a,w-nitrile ester and a,w-diester) was attempted in a cascade
RCM/cross-metathesis sequence involving the initial RCM reac-
tion of 2a leading to 3,6-dihydropyran 3a, followed by a cross-
metathesis reaction with methyl acrylate and acrylonitrile
(Scheme 6). Compound 2a underwent a RCM reaction in the
presence of methyl acrylate (2 equiv) at 1008C in toluene. The
Tandem RCM/Hydrogenation
Having demonstrated the efficiency of the RCM reaction for
the production of various 3,6-dihydropyrans and a,b-unsaturat-
ed lactone derivatives, the tandem[23] RCM/hydrogenation se-
quence[8c,24] was attempted to prepare tetrahydropyran and
lactone derivatives that are also compounds of interest in vari-
ous domains, such as fragrance and pharmacy.[25] For that pur-
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C. Fischmeister, C. Bruneau et al.
the cross-metathesis product 10
in 91% yield. The same reaction
with acrylonitrile turned out to
be more difficult and required
a
higher catalyst loading to
ensure efficient formation of 11.
With 1 mol% of catalyst HII, 3a
and 11 were isolated in 92 and
65% yield, respectively (whereas
with an initial catalyst loading of
0.5 mol%, 3a and 11 were iso-
lated in 91 and 43% yield, re-
spectively). As generally ob-
served, cross-metathesis with
methyl acrylate furnished exclu-
sively the E isomer, whereas the
Z isomer was obtained as the
major product for the cross-
metathesis with acrylonitrile.
Scheme 5. Tandem RCM/hydrogenation transformations.
This cascade or domino protocol
is thus another example where
cascade reaction with methyl acrylate proceeded with full con-
a fine chemical and a polymer precursor are produced effi-
ciently and simultaneously in a one-pot reaction.
version of 2a furnishing the RCM product 3a in 93% yield and
Figure 1. Methyl ricinoleate as a platform chemical.
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Methyl Ricinoleate as a Platform Chemical
Conclusions
We have shown that methyl rici-
noleate can be used as a plat-
form chemical for the synthesis
of a variety of functional com-
pounds of interest both in fine
chemistry and polymer synthesis
(Figure 1). These products were
prepared using efficient olefin
metathesis transformations per-
formed as a single reaction or
by sequential transformations.
These first examples open up
the route towards further utiliza-
tion of methyl ricinoleate for the
production of a broad range of
Scheme 6. Cascade RCM/cross-metathesis transformations.
functional molecules potentially
accessible by the appropriate in-
˙
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Keywords: hydrogenation · lactones · metathesis · renewable
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FULL PAPERS
A. Dupꢀ, M. Achard, C. Fischmeister,*
C. Bruneau*
&& – &&
Methyl Ricinoleate as Platform
Chemical for Simultaneous Production
of Fine Chemicals and Polymer
Precursors
The derivatization of methyl ricino-
leate followed by ring-closing metathe-
sis (RCM) or sequential RCM/hydrogena-
tion and RCM/cross-metathesis lead to
a variety of biosourced compounds of
interest for fine chemistry and polymer
synthesis. 3,6-Dihydropyran, and a,b-un-
saturated lactone derivatives have been
prepared with concomitant production
of polymer precursors. Tetrahydropyran
and lactone derivatives as well as valu-
able monomers in particular polyamide
precursors have also been prepared.
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